Synergistic palladium/enamine catalysis for asymmetric hydrocarbon functionalization of unactivated alkenes with ketones

Abstract

Synergistic palladium and enamine catalysis was explored to promote ketone addition to unactivated olefins.

Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

“…During the past 5 years, our laboratories have developed a variety of transition-metal-catalyzed, three-component directed alkene 1,2-difunctionalization reactions facilitated by the 8aminoquinoline (AQ) auxiliary, a strongly coordinating bidentate directing group. Using this strategy we and others have reported examples of hydrofunctionalization [21][22][23][24][25][26][27][28][29][30][31][32][33] , dicarbofunctionalization [34][35][36][37][38][39] , carboamination 40,41 , and carbo-/aminoboration [42][43][44][45] , among other transformations 46,47 (Fig. 1c).…”

Mapping Ambiphile Reactivity Trends in the Anti‐(Hetero)annulation of Non‐Conjugated Alkenes via PdII/PdIV Catalysis

“…In particular we targeted ortho ‐iodobenzophenone, which was found to be unreactive under various reaction conditions, including those in Table 2. A dual Pd II /organocatalytic activation strategy [12h,i] was applied to enhance the nucleophilicity of the α‐carbon (Table 6). A high‐throughput screen identified CsOPiv and toluene as the base and solvent of choice (see Supporting Information).…”

Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis

“…[41] In the same year, a similar synergistic Pd/enamine catalyzed asymmetric addition of ketones 13 to unactivated olefins 16 was reported by Shi and co-workers (Scheme 10). [42] The high level of stereo- chemistry was solely controlled by the chiral amine. Moreover, γ-addition products 17 with good yields and efficient stereochemical control (up to 96 % ee) were obtained by the synergistic effect of Pd(II) catalyst and diphenylprolinol.…”